US1761641A - Metallurgical process - Google Patents

Description

.lime 3, 193. R. D. PIKE I METALLURGICAL PRCESS.

' Filed Feb.'11. 19.26

IIIIvII .L

INVENToR.

ATTORNEYS.

I.. I I

closed in In Patented Juney 3, 1930 PATENT @FFICE ROBERT .'D. 'IKE, 0F PIEDMONT, CALIFORNIA METALILURGICAL PROCESS Application led February 11, 1926. Serial No. 87,4509..

This invention relates to a cyclic process for the treatment of sulphide ores for the recovery of the metallic content, and more particularly to a process of the nature disapplication Serial Number 58,012, tiled eptember 23, 1925. A

The object of the present invention is to make possible -the treating of certain classes o relatively clean copper concentrates which may contain appreciable amounts of Ca, Mg,

and Al. in such manner that but-little discard of the solution becomes necessary in carrying out acyclic process of the general `nature disclosed in the above-mentioned api plication. A further object is the production of electrolytic iron from sulphide ores.

Mypresent invention' provides a practical method of carrying out such a cyclic process with little or no discard of the electrolyte, and replacing unavoidable losses of electrolyte in a cheap and convenient manner, as well as other novel and useful features. The electrolytic iron resulting from this process is of higher purity than has hitherto been produced by a commercial process, having the following analysis:

Carbon .006 or less Sulphur .007 or less Copper .006 or less with an entire absence of phosphorus, silicon,

manganese, nickel, cobalt, cadmium, arsenic,

lead, tin, and zinc.

In the accompanying drawing Ishow the application o a preferred form of low sheet to a copper concentrate of the ollowmg approximate analysis:

0.10 oz. per ton the more inely-ground the concentrate the better.

The copper mineral in this concentrate is composed substantially of two-thirds bornite and one-third chalcopyrite.

However, I do not wish to be understood as limiting my invention to the particular case described, because a considerable variation may be permitted in the class of mineral treated as well as in the nature of the solutions employed and the steps followed without departing from the spirit of my .invention, which I believe to be broad and basic in its nature in view of the prior known art.

Referring to the flow sheet, 1a is an agitator shown conventionally as a tank with with a propeller. The tank is preferably lined with acid-proof stone ware and the propeller and shaft rubber covered. Into this tank is introduced a continuous-stream of leach liquor containing about 10% total iron as chloride, and of this total iron about half or'5% as ferric chloride. A continuous stream of the above-mentioned concentrates is also introduced into tank l, and live steam is introduced in suiicient amount to maintain the-temperature at 100 to 105 centigrade. The relative dow of leach and concentrate is so proportioned that the eilluent will contain 1.2% to 1.3% of ferrie iron. The .size of the tank is so proportioned that the time of residence is about 3 hours. The stream of thin pulp then goes to a similar but smaller agitator 1, where a continuous stream of pyrrhotite is added, so as to reduce the ferrie iron to .2%. The tank 1" is so proportioned that the time of residence is one to two hours. My reason for splitting the leaching operation into two stages employing pyrrhotite in the second stage lis ,that by this means I efect a higher extraction of copper from the concentrates than if the latter were depended upon to complete the reduction of the solution. I ind that 'tor each pound of concentrate about .2 pound of pyrrhotite is required-varying somewhat with variations in the grade of both concentrate and pyrrhotite.

The ettluent from the tank 1b ,passes to tlter press 2. The euent from the filter contain about 5% of ferric chloride.

press 2 contains in solution about 90% of the copper and 90% of the silver in the original minerals, as well as about 65% of the iron. I may now introduce chlorine to make up for unavoidable losses usually amounting to about .1 to .3 pound Cl per pound of electrolytic iron produced in a later stage of the process by diverting the necessary portion of the efiiuent from the filter press 2 and treating with gaseous chlorine in a suitable apparatus 2. The amount of electrolyte so diverted is proportioned so that when the required amount of chlorine has been introduced the resulting liquor will The chlorinated liquor then goes back to 1a. Make up chlorine can be added by introducing same into the leach tank 1, but if'this is done some of the chlorine will be employed in oxidizing sulphur to sulphate. The balance or major part of the liquor from the filter press 2 continues on through suitable apparatus conventionally shown as treating vessels 3, 3", 3c, for precipitation of silver. This can be accomplished by precipitating silver on copper in any well-known manner.

The liquor, after silver precipitation, passes to suitable receptacles 4.a, 4", for precipitation of copper on iron. The method illustrated is as follows: Tank Litis filled with solution heated to O to 80 centigrade and slightly acidulated with II2S04 to pH about 2.5 and the requisite amount of sponge iron added to effect complete precipitation l of the copper. The copper is then allowed to settle, and the clear liquor decanted off. The cement copper is passed through a filter 5 and the efiiuent returned to either receptacle 4 or 4b because it may contain traces of redissolved copper. The main flow of liquor passes through a clarifying press 6 and then through a gas-treating tower 7 where it is treated with I-I2S to `precipitate traces of Zn and possibly other impurities. With regard to Zn, I find it desirable to limit the content of this metal to 1% or less in the ores and concentrates received by the plant; but I have discovered that as much as .1% Zn remaining in the solution after the treatment with HQS results in practically no contamination of the iron with Zn. The liquor then passes through filter 8, where any sulphides which were formed in gastreating tower 7 are filtered out. The purified liquor then passes through an evaporator 9 of suitable design to restore the specific gravity of the liquor to about 1.3 to 1.35. The efiiuent of concentrated liquor. from the evaporator then passes to correction tanks 10 and 10". An accurate determination of copper is made at this point, and if any analytical trace is found above .01%, a small amount of sponge iron is added after correcting the acidity to pII=2.5 by addition of HZSO, and the temperature of the solution being maintained at 70 to 80 centigrade the last trace of copper is precipitated. At this point it will usually be necessary to add some CaCl2 to keep the S04 content of the solution at the equilibrium point represented by the solubility of CaS04 in these solutions. I have found such equilibrium point to be about .15% of S04. The addition of CaClz in this manner precipitates artificial gypsum and puts chlorine into the solution, and by properly controlling the addition of S04 as described hereafter, all of the chlorine losses can be made up in this manner by addition of CaCl2 if desired; and if this practice is followed, obviously it will be unnecessary to add chlorine gas as above described. The choice between calcium chloride and chlorine gas for making up chlorine losses rests to some extent on economic grounds; but I have found that the voluminous precipitation of calcium sulphate (gypsum), which is formed when all of the chlorine loss is made up by the addition of calcium chloride, is very useful in the precipitation of traces of colloidal carbon and sulphur from solution, and consequently in producing an electrolytic iron in the subsequent step of the process which is exceptionally vfree from these impurities.

The liquor which leaves tanks 1011 and 10b is completely purified, and has only to be passed through a filter 11 before going to a tank 12 which is the electrolyte storage for the electrolytic iron department. The electrolyte then passes through heater 13 and goes to electrolytic iron cell 14. This is of the diaphragm type vwith insoluble graphite anodes. A portion of the catholyte goes to the sump 15 and is circulated back to the tank 12. The return circulation of catholyte from the electrolytic iron cells contains small i amounts of basic salts of iron in suspension and these are filtered out by providing tank 12 with a sand filter false bottom, not shown, or by other suitable means, thus insuring a feed of clear electrolyte to the cells. The anolyte leach goes to the sump 14a.

Returning now to a consideration of the tails from the filter 2. These contain about 20% of free distillable sulphur and about 10% of insoluble matter. I have found that a very clean separation can be made between the minerals and sulphur on one hand and the insoluble matter on the ot-herhand,by flotation if desired, in a suitable flotation apparatus, not shown. It will usually be considered justifiable to carry out such flotation on economic grounds. Whether flotation be employed or not, the solids may next be treated for recovery of refined sulphur by distillation in retorts 18, the sulphur being condensed in 19. Steam may be employed, if desired, to assist distillation. The distillation of sulphur may be omitted entirely if desired. The solids, either direct from filter press 2 or after flotation, or distillation, lor both, go next toa multiple hearth roaster 20. Here the roasting may beso conducted by wellknown means as to produce just the proper amount ofS04 which may be desired to precipitate CaCl2 in the correction tanks 10a and 10". If chlorine losses are being made up" from' gaseous chlorine, then no S04 should be produced in this step, and all copper should be roasted to oxide A small amount.of`-S04. is always inadvertently formed in leaching tanks 1a and 1b, and this will usually require the addition of a small amount of CaCl2 in tanks 10a and 10b, although lime occurring naturally in the concentrates will act to precipitate S04.

VAn important discovery in connection with this invention is that soluble Mg and Al, Na and K which would ordinarily go into solution as chlorides form insoluble basic salts, and the precipitation of these base salts, together with precipitation of lime, prevents the building up of these impurities in the solution without its being necessary to make a systematic discard. I have found that, after running my process for over 40 complete closed cycles and in spite of the fact that a considerable part of the Ca, Mg, and Al in the concentrates and pyrrhotite is soluble in ferrie chloride leaches, the concentration of Mg is less than .1%, and of All less than .01%,

la 1%, K .1%, and the Ca maintains its expected concentrationv based upon the gypsum solubility, namely .3% to .5%. An addi- 517 tional source of S04 ion to those mentioned is found in the manufacture of the ILS which, as above stated, is used in purifying the solution, and particularly for the removal of Zn. rIhis HZS can be made by treating pyrrhotite (FeS) with HZSO, in suitable apparatus, not shown, and thel resulting FeS04 solution can be added to the main flow of liquor just prior to its entering the evaporator. I have found that, considering the S04 which it is possible to produce by roasting the 0u remaining after the first or chloride leach to CuS04, the S04 which is made by spontaneous oxidation of sulphur in the first or chloride leach, and that which may be recovered as a by-product from the manufacture of HZS, I can provide all make up chlorine from CaCl2 added in the correct-ion tanks, as above described, to the extent of .1 pound to .8 pound per pound of electrolytic iron, which will usually be more than enough to cover actual losses in the operation of the cycle. Also in adding this amount of CaCl2 a free filtering but very voluminous precipitate of artificial gypsum which is a highly efficient cleaner for removing` impurities from solution by absorption and adsorption, is formed. This reaction may be closely compared to the cleansing action of precipitated 09.008 1n purifying beet sugar juices.

I have further found that after roastingvin 17, the effluent joining the stream of remaining anolyte leach and going to the tank 1B. The tails from the filter 17 contain practically all of the gold occurring in the concentrates and pyrrhotite, and this may be recovered, if desired, by any suit-able known means. A

The iron produced by this process is of extreme and novel purity. The sum of the impurities 0, S, P, Si, and Mn, is less than 015%, and this result makes available for commercial use a purer form of iron than has hitherto been available. Iron of this unique purity has great value in the manufacture of electromagnetic alloys of types which are useful in theelectrical industry.

An alternative method of effectin a high extraction of the metals, which is useul when a high iron extraction is the principal end sought, is based upon my discover that, if I take the solid residues after the distillation of same for the recovery of sulphur, a certain further extraction of metal will result if this residue be again treated with. fresh anolyte leach and without` roasting. This further extraction is also assistedbyregrinding with or without distillation of sulphur. It is usually more advantageous to roast as'described when treating copper concentrates; but if pyrrhotite, for example, carrying say 1.5 to 2% 0u is the ore being treated and the main product is electrolytic iron with-Cu as a by-product of secondary importance, then the roasting step is not necessary. This isv true because a 90% recovery of the 0u, which is readily obtained, is satisfactory Vin such a case, and the roasting does not result in recovery of any more iron. Any iron which is to be recovered from the pyrrhotite and produced as electrolytic iron mustbe dissolved from the pyrrhotite as such without roasting, because iron oxide is not soluble in ferrie chloride.

If pyrrhotite is the raw material employed and the roasting step is eliminated, as indicated, some other means has to be employed for supplyin S0.1 to the cycle. Additional amounts of 04 can be formed by blowing air through the leaching tank la. However, the roasting step will usually be the most suitable method for adding S04 to the cycle, and in carrying out such a step it is not necessary either before or after recovery of their sulphur by distillation, but other ores or concentrates can be employed, in whole or in part, such, for example, ascopper concentrates. If the residue from the leach in 1z is first treated for distillation of S and then reground, a dry grinding unit (not shown) l to employ tails from the first chloride leach,

is employed, and the reground tails are again treated With strong leach, the filtrate going to l, and the tails being reserved for recovery of precious metals, if desired.

Having thus described my invention, What I claim as new and desire to secure by Letters Patent is l. A cyclic'process for treating sulphide ores for recovery of their metallic content which consists in leaching with a hot solution containing ferrie chloride, precipitating from said solution substantially all metals except iron, adding calcium chloride to the solution, electrodepositing iron and regenerating the erric chloride leach, roasting the tails from the leaching operations, leaching the cinders from the roast with all or a portion of the regenerated ferrie leach before said leach is returned to the first-mentioned leaching operation, and so controlling the oxidation of sulphur to sulphate in the cycle that sufficient of the latter ion will be formed to precipitate impurities which form relatively insoluble sulphate compounds.

2. A-cyclic process for treating sulphide ores for recovery of their metallicjcontent and sulphur, which consists in leaching with a hot solution containing ferrie chloride, precipitating from said solution substantially all metals except iron, adding calcium chloride tothe solution, electrodepositing iron and regenerating the ferrie chloride leach, distilling sul hur from the tails from the leaching opera ions, roasting the residue after distillation, leaching the cinders from the roast with all or a portion of the regenerated ferrie leach before said leach is returned to the firstmentioned leaching operation, and so con-k pounds.

3. A cyclic process for treating sulphide ores for recovery of their metallic content and sulphur, Which consists in leaching With a hot solution containing ferrie chloride, precipitating from said solution substantially all metals except iron, adding calcium chloride to the solution, correcting acidity to the optimum point for electro-deposition of iron, electrodepositing iron and regenerating the ferrie chloride leach, subjecting the tails from the leach to flotation to concentrate their metallic content, roasting the concentrates, leachinglthe cinders from the roast with all or a portion of the regenerated ferrie leach before said leach is returned to the firstmentioned leaching operation, `and so controlling the oxidation of sulphur to sulphate in the cycle that suiiicient of the latter ion will be formed to precipitate impurities Which form relatively insoluble sulphate compounds.

4. A cyclic process for treating sulphide ores for recovery ottheir metallic contenty which consists in leaching With a hot solution containing ferrie chloride, diverting a, portion of solution after said leach, adding chlorine gas and returning the chlorinated liquor to the leach, precipitating from the net advance of solution substantially all metals except iron, electrodepositing iron and regenerating the ferrie chloride leach, roasting the tails from the mentioned leaching operation, leaching the cinders from the roast with all or a portion of the regenerated :terric leach before said leach is returned to the firstmentioned leaching operation, and so controlling the oxidation of sulphur to sulphate in the cycle that suthcient of the latter ion will be formed to precipitate impurities which form relatively insoluble sulphate compounds.

5. A cyclic process for treating sulphide ores for recovery of their metallic content which consists in leaching With a hot solution containing ferrie chloride, diverting a portion oi' solution after said leach, adding chlorine gas and returning the chlorinated liquor to the leach, precipitating from the "Ire-1t: advance ot solution substantially all nietals except iron, electrodepositing iron and regenerating""tlie -ferric chloride leach, roasting the tails from the mentioned leaching operation, leaching the cinders from the roast with all or a portion of the regenerated ferrie leach before said leach is returned to the` first-mentioned leaching operation, and so controlling the oxidation of sulphur to sulphate in the cycle that suiicient of the latter ion will be formed to precipitate impurities which form .relatively insoluble sulphate compounds, andadding calcium chloride to prevent accumulation of sulphate ion.

6. lhe steps in a process for treating sulphide ores for recovery-oit' their metallic content which consists in leaching the ore with a leach containing ferric chloride, roasting the tail, and thenfurther leaching the cinders with ferrie chloride leach for increasing the extraction ot copper and other metals.

7 The steps ina cyclic process for treating sulphide ores for. recovery of their metallic content which consist in leaching the ore with a leach containing ferrie iron and substantially no added acid, roasting the tails, and th-eniurthcr treating the cinders With substantially the same leach liquor as employed in the first-mentioned leach for increasing the extraction of copper and other metals.

8. The steps in a cyclic process for treating sulphide ores for recovery of their metallic content which consist in forming Within the cycle suiicient sulphate ion to precipitate all impurities which form insoluble compounds with the sulphate ion.

9. The steps in a cyclic process for treating sulphide ores for recovery of their metallic content whichconsists in forming Within the cycle suliicient sulphate ion to precipitate all impurities which form insoluble compounds with the sulphate ion, and preventing the accumulationqof sulphate ion by addition of calcium chloride.

, 10. The step in a cyclic process for treating sulphide ores for recovery of their metallic content-Which consists in making up losses of chlorine from the electrolyte by adding calcium chloride to the electrolyte and precipitating the calcium by sulphate ion.

11. The step in a cyclic process fortreating sulphide ores or recovery of their metallic content which consists in maintaining sulphate ion in the electrolyte at a predetermined concentration by precipitating all in excess of the said concentration as calcium sulphate by adding calcium chloride to the electrolyte. I

12. The step in a cyclic process for treating sulphide ores for recovery of their metallic content for replacing chlorine losses in the electrolyte, which consists in withdrawing a portion of the electrolyte, treating the same with chlorine gas, and returning the chlorinated liquor to the leaching step of the c c e.

y13. The step in a cyclic process for treating sulphideores for recovery of their metallic content including electrolytic iron which consists of removing colloidal carbon and sulphur from solution by causing to 'form in said Vsolution a voluminous precipitate of artificial gypsum, by interaction of added calthe solution. 14. The steps in a cyclic process for treating sulphide ores for the recovery of electrolytic iron, other metals, and sulphur, which consist in subjecting the ore to the action of a solution containing ferrie iron, liltering?, subjecting the residue to distillation for recovery of elemental sulphur, and again leaching the residue for the further solution oi metals with a leach containing ferrie iron.

, 15. The steps in a cyclic process for treat-l cium chloride with surplus sulphate ions in ing sulphide ores for the recovery of elec-l trolytic iron, other metals, and sulphur, which consist in subjecting the ore to the action of a solution containing ferrie iron, iiltering, subjecting the residue to distillation for recovery-of elemental sulphur, regrinding the residue after distillation, and again leaching the reground residue with a leach containing ferrie iron tion of metals.

16. ln a cyclic process for treating sulphide orev for the recovery of electrolytic iron and other metals, the steps ont making up chlorine losses by the reaction of CaCl2 with SQL ion in the electrolyte, and controlling the amount oi S94, ion formed" in the leaching step with iem'ic chloride leach lby introducing a regufor the further solutaining ferrie chloride, electro-depositin iron, and regenerating the ferrie leach, an adding sulphate iron to the cycle in an amount suiicient tov-maintain aconcentration of less than .3%. j

18. A cyclic process for treating sulphide ores for -recovery of electrolytic iron,'which consists in leachin with a hot solution containing ferric ch oride, electro-depositing iron and regenerating the chloride leach and adding sulphate ion to replace that precipitated as insoluble sulphates in the cycle.

19. A cyclic process for treating sulphide ores for recoveryof electrolytic iron, which consists in leaching withy a hot solution containing ferric chloride, adding calcium'chloride to make up chlorine losses, electro-dey positing iron and regenerating the chloride leach, and adding sulphate ion to replace that precipitated as insoluble sulphates in the cycle.

20. A cyclic process for treating `sulphate ores for the recovery of electrolytic iron,

which consists in leaching with ahot solution containing ferrie chloride, adding gaseous chlorine to the liquorin an amount sutlicient to make up chlorine losses inthe cycle, electro-depositing iron and regenerating the chloride leach and maintaining the concentration of sulphate 'ion at a substantially constant level by forming insoluble sulphate pre- 'cipitates with the surplus.

normar D. PIKE.

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